Satellites of the Dipole-Forbidden Transitions to the Low-Lying 2S1/2 and 2D3/2,5/2 Excited States of K, Rb, and Cs Atoms in the Spectra of Gas-Phase Mixtures with CF4
Vadim A. Alekseev, T. A. Vartanyan, Anatoly S. Pazgalev +1 more
The luminescence excitation spectra of the D1 resonance line of atoms K, Rb, and Cs in gas mixtures with CF4 are found to contain satellite transitions, which correspond to the transition of an atom to the states (n – 1)d 2D3/2,5/2 and (n + 1)s 2S1/2, where n = 4, 5, and 6 for K, Rb, and Cs, respectively, with the simultaneous excitation of CF4 molecule vibrations at the IR active mode frequency ν3 with a quantum energy of 1283 cm–1. These satellite transitions are A(ns 2S1/2) + CF4(ν3 = 0) + hν → A((n – 1)d 2D3/2,5/2) + CF4(ν3 = 1) and A(ns 2S1/2) + CF4(ν3 = 0) + hν → A((n + 1)s 2S1/2) + CF4(ν3 = 1), where A = K, Rb, and Cs. The appearance of an optical coupling between the upper and lower states of these asymptotically (at $${{R}_{{{\text{A}} - {\text{C}}{{{\text{F}}}_{4}}}}}$$ → ∞) forbidden transitions is shown to be caused by the interaction of the dipole moment of the ν3 = 1 ↔ ν3 = 0 vibrational transition in the CF4 molecule with the dipole moments of the electronic transitions np 2P1/2,3/2 ↔ (n – 1)d 2D3/2,5/2 and np 2P1/2,3/2 ↔ (n + 1)s 2S1/2 in an alkali metal atom; as a result of this interaction, the upper state of the satellite transition acquires admixtures of the A(np 2P1/2,3/2)CF4(ν3 = 0) resonance states.
Journal of Experimental and Theoretical Physics•Sep 1, 2023•0 citations